Accounts of Chemical Research最新文献

{"title":"Perovskitoids as Functional Materials.","authors":"Isaiah W Gilley, Taylor E Wiggins, Edward H Sargent, Mercouri G Kanatzidis","doi":"10.1021/acs.accounts.5c00240","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00240","url":null,"abstract":"<p><p>ConspectusFollowing the development of perovskite solar cells, the synthesis of hybrid Pb, Sn, and Ge halides exploded in popularity, with more than 3000 such crystal structures uploaded to the Cambridge Structural Database since the start of 2015. This synthetic interest has been accompanied by demonstrations of the materials' efficacy, such as solar cells, light-emitting diodes, and detectors. Though perovskites are the dominant focus for these optoelectronics applications, they comprise just over half of the 3000 structures mentioned. The nearly 1400 remaining nonperovskite materials include face- and edge-sharing structures like δ-FAPbI<sub>3</sub> and δ-CsPbI<sub>3</sub>, often seen as undesirable products of failed perovskite syntheses. Indeed, all-face- and all-edge-sharing structures have had little success as optoelectronics, but a subset of these nonperovskites has demonstrated some success as functional materials. We call this subset perovskitoids, a class of materials defined, like perovskites, by their structural connectivity. While both perovskites and perovskitoids have corner-sharing octahedra in their crystal structures, perovskitoids can also contain face- or edge-sharing octahedra. This mixed sharing lends perovskitoids a much greater degree of structural diversity than is present in materials with a single sharing type, and the resulting materials combine properties of their respective connectivities.As corner-, edge-, and face-sharing octahedral connections require different M-X-M bond angles, the degree of orbital overlap between consecutive octahedra varies with the sharing type, resulting in a strong dependence of perovskitoids' bandgaps on their specific connectivities. This dependence enables bandgap modulation by varying fractions of corner-, edge, and face-sharing within perovskitoids, accessing bandgaps that, for perovskites, would require halide mixing or dimensional reduction. The added edge- and face-sharing connections in perovskitoids also lend the materials greater air, water, and thermal stability than their perovskite counterparts by virtue of the added redundancy of the octahedral connections.In this Account, we give an overview of the structures, properties, and applications of perovskitoids, focusing on the ways in which they resemble and differ from perovskites. Specifically, examples of common types of perovskitoids are presented along with a summary of the relative effects of corner-, edge-, and face-sharing connectivity on their bandgaps, luminescence, and stability. Following is a discussion of applications of perovskitoids, highlighting our groups' previous work on perovskitoid phosphors, photodetectors, X-ray detectors, γ-ray detectors, capping layers for perovskite solar cells, and wide bandgap solar absorbers. Subsequently, we discuss strategies for improving upon the optoelectronic properties of existing perovskitoids, focusing on the synthesis of perovskitoids with high fractions of corner-","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":""},"PeriodicalIF":16.4,"publicationDate":"2025-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144511239","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Underscoring Covalent-Organic Frameworks As Nanoengines for Zinc Anode Protection Coating.","authors":"Can Guo, Pan Xue, Fengxue Duan, Yifa Chen, Ya-Qian Lan","doi":"10.1021/acs.accounts.5c00226","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00226","url":null,"abstract":"<p><p>ConspectusRechargeable aqueous zinc-ion batteries (AZIBs) have emerged as promising energy storage systems owing to their high energy density, environmental benignity, and low cost. Nevertheless, the rough surface of the Zn metal anode can easily induce uncontrolled dendrite growth and parasitic reactions, which will limit the large-scale commercial applications of AZIBs. Owing to the diverse active sites and porous channels of covalent-organic frameworks (COFs), the exploration of COFs in this field affords a novel perspective in tackling the bottlenecks encountered through the anode of AZIBs. Based on reported works, this review summarizes the functions of COFs as nanoengines to manipulate the Zn²⁺ flux, hydrogen evolution, dendrite growth, and the electric field at electrode/electrolyte interface when applied as functional coatings. It also concludes the construction strategies of functional COFs coating and delves into strategies for protecting the Zn anode, with an emphasis on modulating Zn deposition dynamics and minimizing side reactions at the electrode/electrolyte interface. It further provides an evaluation of the current challenges and future expectations of AZIB, aiming to enhance their viability for grid-scale energy storage solutions.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":""},"PeriodicalIF":16.4,"publicationDate":"2025-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144504060","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Kinetics, Thermodynamics, and Emergence in Stereoediting Reactions.","authors":"Gino Occhialini,Alison E Wendlandt","doi":"10.1021/acs.accounts.5c00299","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00299","url":null,"abstract":"ConspectusThe selective formation of one stereoisomer over another is a long-standing challenge in organic chemistry. Conventionally, the configuration of a stereogenic center is defined during bond forming molecular assembly steps and thereafter treated as a static component of the molecular structure. One isomer is often more accessible than others, because it can be obtained directly from natural sources, because synthetic strategies to access certain stereochemical patterns are more efficient than others, or because substrate-based steric and electronic biases preclude certain reaction outcomes. In such cases, the ability to revise the stereochemistry without altering the underlying molecular skeleton could parlay more accessible products directly into more challenging targets.In this Account, we describe our efforts to develop stereocenter editing tools to enable the interconversion of stereoisomers with a predictable and tunable selectivity. Stereoediting methods developed by our lab leverage radical intermediates accessed by sequential H atom abstraction and donation steps promoted by a range of different H atom transfer reagents. Modern photoredox methods enable access to reactive radical intermediates under mild reaction conditions, serve as an orthogonal stimulus to induce dynamic character from otherwise static structures, and provide ample fuel to drive contra-thermodynamic product composition when mechanistically feasible.The first methods developed by our lab targeted secondary alcohol stereogenic centers located ubiquitously in complex chiral molecules. By varying catalyst identity and reaction conditions, product distributions can either reflect a thermodynamic equilibrium or reach an out-of-equilibrium steady state defined by kinetic factors. In the latter case, catalyst control enables contra-thermodynamic product distributions to form and offers the best prospects for tunable site- and stereocontrol. Our laboratory has been particularly interested in applications of stereoediting in rare sugar synthesis where innovative solutions are required to address the site-selectivity challenges presented by minimally protected glycan substrates.Subsequent efforts in our laboratory have led to the development of stereoediting methods targeting unactivated tertiary stereogenic centers for which there are few other methods or synthetic routes for stereorevision. Here, stereoediting methods offer substantial flexibility for molecular construction and can formally extend the scope of stereochemical outcomes accessible from powerful existing synthetic methodologies. Finally, we have sought to extend the mechanistic principles governing catalyst-controlled stereocenter isomerization into more general classes of constitutional isomerization, including a synthetically versatile contra-thermodynamic positional alkene isomerization reaction leveraging many of the same elementary steps.Like other transformations within the \"editing\" superfamily, ste","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"48 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2025-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144488251","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exploring On-Surface Synthesis under Mild Conditions.","authors":"Yi-Qi Zhang,Jonas Björk,Johannes V Barth","doi":"10.1021/acs.accounts.5c00157","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00157","url":null,"abstract":"ConspectusBottom-up approaches combining tailor-made molecular precursors and surface-mediated reactions under ultrahigh-vacuum (UHV) conditions attracted significant attention over the past decade as a promising strategy for synthesizing novel, functional, molecule-based materials. These methods have been remarkably successful in creating unconventional covalent products with atomic precision, though largely focusing on one-dimensional (1D) polymeric products. Extending the established protocols to synthesize two-dimensional (2D) covalent architectures presents a major challenge, primarily due to high annealing temperatures required that often entail competing reactions, high defect densities, and structural degradation.In this Account, we highlight the exciting potential of low-temperature (LT) on-surface reactions as an alternative pathway and discuss their largely unexploited capabilities. We summarize major recent advances, focusing on coinage metal surface-assisted chemical transformations at mild conditions in UHV, proceeding frequently near or below room temperature (RT). Special emphasis is placed on alkyne derivatives, either alone or combined with other functional groups, identified as versatile building blocks for next-generation carbon-rich nanomaterials such as graphyne or graphdiyne and their metalated derivatives, which offer immense potential for future technological applications.We discuss four major pathways for initiating LT on-surface reactions of alkyne species, following largely the chronological order of their discovery, and merging insights from high-resolution scanning probe microscopy, X-ray spectroscopies and density functional theory calculations: (i) Conversions catalyzed by in situ generated species and extrinsic elements; (ii) quantum tunneling-mediated reactions; (iii) reaction pathways involving surface-assisted radical or hydrogen transfer processes; and (iv) gas-mediated on-surface reactions. These and other selected examples of LT synthesis protocols offer significant advantages in terms of high selectivity and efficiency, notably enabling the controlled synthesis of extended, regular 2D organometallic and covalent compounds or architectures, and bearing promise for a multitude of all-carbon scaffolds, which currently remain challenging. We aim to inspire the development of functional robust nanoarchitectures with long-range order and atomic-scale precision, contributing to the advancement of molecule-based materials for diverse technological applications.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"40 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2025-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144488205","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tailoring Light-Matter Interactions in 2D Semiconductors.","authors":"Ona Ambrozaite,Reynolds Dziobek-Garrett,Thomas J Kempa","doi":"10.1021/acs.accounts.5c00179","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00179","url":null,"abstract":"ConspectusTwo-dimensional (2D) crystals have had a sweeping influence on the condensed matter physics and materials science communities for over two decades. Their thinness and ability to be configured into layered and twisted heterostructures has enabled 2D crystals to become a platform material of choice to uncover many intriguing phenomena, including superconductivity, the fractional quantum anomalous Hall effect, spin textures, strain domain walls, and distinct spin-valley transitions. This versatility is on display in 2D semiconductor monolayers, which exhibit strong light-matter coupling to a rich host of excitonic states and valley selective transitions. The optical physics of 2D semiconductors is tunable through manipulation of their structure, chemical composition, mutual orientation in superlattices, and strain. Together, such adjustments give rise to a plethora of exciting applications in optics, spintronics, and quantum sensing. Our contributions to the 2D materials community have focused on developing chemical strategies for precision nanostructure synthesis, elucidating emergent optical phenomena through detailed spectroscopic analysis, and creating new 2D heterostructures that support the localization and manipulation of quasiparticle states. This Account examines selected aspects of our recent work on tailoring light-matter interactions in 2D semiconductors. We discuss how synthetic manipulation of a 2D crystal's dimensions, edge structure, strain state, and coupling to other molecular species and lattices renders specific properties. Through this article we wish to draw attention to the rich chemistry of 2D crystals and the active role chemistry should play in opening new avenues of research in 2D materials.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"12 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2025-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144370425","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"ATR-SEIRAS for Single-Atom Electrocatalysis","authors":"Yinyin Wang, Jie Ding, Chenliang Su, Zheng Shen, Bin Liu","doi":"10.1021/acs.accounts.5c00303","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00303","url":null,"abstract":"Single-atom catalysts (SACs) represent a revolutionary paradigm in heterogeneous catalysis and display exceptional atom utilization efficiency with well-defined active sites. These distinctive characteristics position SACs as pivotal materials for advancing electrochemical energy conversion and storage technologies. The active center atoms are typically anchored by coordination with oxygen (O), nitrogen (N), and other functional groups on the surface of the supports. When precisely anchored onto tailored supports, these isolated active centers offer considerable promise for enhanced catalytic activity and selectivity. Nevertheless, the inherent complexity of the multistep proton-coupled electron transfer processes in electrochemical energy conversion and storage systems presents major challenges for the mechanistic elucidation and rational design of catalytic architectures to optimize reaction kinetics. Recent advancements in <i>in situ</i>/<i>operando</i> characterizations, most notably attenuated total reflection–surface-enhanced infrared absorption spectroscopy (ATR–SEIRAS), have greatly stimulated SACs research. ATR–SEIRAS amplifies the vibrational signal at the interface, enabling real-time tracking of transient interfacial species at submonolayer concentrations. Moreover, it simultaneously captures the dynamic structural evolution of single-atom motifs during the catalytic cycles.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"45 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2025-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144371256","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Induced-Fit Chiral N-Heterocyclic Carbene Ligands for Asymmetric Catalysis","authors":"Zi-Chao Wang, Shi-Liang Shi","doi":"10.1021/acs.accounts.5c00304","DOIUrl":"https://doi.org/10.1021/acs.accounts.5c00304","url":null,"abstract":"Asymmetric transition-metal catalysis stands as a cornerstone in the construction of molecules with stereogenic centers, profoundly impacting modern organic synthesis. Over the past decades, catalytic asymmetric synthesis has witnessed remarkable advancements, largely driven by the development of sophisticated chiral ligands. While chiral phosphorus ligands have experienced rapid growth and widespread application, chiral <i>N</i>-heterocyclic carbene (NHC) ligands remain underexplored, primarily due to the inherent challenges in designing and synthesizing suitable chiral frameworks. Given the unique topology and modular steric environment of NHCs, the development of novel NHC ligands holds significant promise.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"15 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144319310","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"","authors":"","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 12","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":16.4,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/arv058i012_1947745","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144422773","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"","authors":"Bo Chu,&nbsp;Haoke Zhang*,&nbsp;Xinghong Zhang* and Ben Zhong Tang,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 12","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":16.4,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.accounts.5c00251","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144422776","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"","authors":"","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 12","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":16.4,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/arv058i012_1947746","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144343169","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}